Anionic detergents of sulfoalkyl-carbamate esters



US. Cl. 260-481 6 Claim! ABSTRACT OF THE DISCLOSURE The disclosure relates to a new series of sulfoalkylcarbamate esters, of alkoxylated higher primary and secondary aliphatic alcohols of from 8 to 20 carbon atoms and of alkoxylated alkylated phenols, having detergent characteristics, of the general formula RooH2('3H)..- 'l-I I- om)xomsoaM where n is an integer of from 3 to 150.

This invention relates to a new series of sulfoalkyl carbamate esters, of alkoxylated higher primary and secondary aliphatic alcohols of from 8 to 20 carbon atoms and of alkoxylated alkylated phenols, having excellent detergent characteristics.

In our pending application Ser. No. 585,814, filed on even date, we disclose the preparation of a new series of sulfoalkylcarbamate esters of lower alkyl Cellosolves, lower primary aliphatic alcohols and of alkylene oxide adducts of said alcohols having excellent solubility in concentrated alkalies and excellent cotton wetting properties. The invention of the pending application diifers from the present case in that in the latter we employ a chloro formate ester of an alkoxylated primary or secondary aliphatic alcohol of from 8 to 24 carbon atoms or a chloroformate ester of an alkoxylated phenol as the hydrophobic function. In the reaction of the hydrophobic function with a hydrophilic function, such as 2-aminoalkyl sulfonic acid salt or an N-alkylamino alkane sulfonic acid salt, we obtain anionic detergents instead of alkali soluble cotton-wetting agents. This difference, which is surprising and unexpected, is due to the hydrophobic function, i.e., alkoxylated primary or secondary aliphatic alcohol of from 8 to 24 carbon atoms or an alkoxylated alkylated phenol wherein the alkoxy group ranges from 3 to 150 units. While the anionic surfactants of the present invention do not display excellent cotton-wetting properties (mercerizing agents in concentrated alkaline solutions, nevertheless they show excellent detergent properties and are compatible with fatty acid soaps and other ionic or nonionic surfactants. The detergency of the sulfoalkyl carbamate esters of the present invention is equivalent to that of a fatty acid soap such as sodium laurate and sodium salts of other higher fatty acids.

In providing the anionic detergents of the present invention, we react 1 mole of an alkoxylated primary aliphatic alcohol or a secondary aliphatic alcohol of from 8 to 24 carbon atoms containing from 3 to 150 alkyleneoxy units, or 1 mole of an alkoxylated alkylated phenol containing from 3 to 150 alkyleneoxy units with a molar excess of phosgene (carbonyl chloride) at temperatures of about 10 C. to 70 C. for a period of time ranging from 2 to about 2 /2 hours, during which the phosgene reacts with the hydroxyl function to yield a chloro-substituted formic acid ester of the alkoxylated primary or secondary alcohol and alkoxylated alkylated phenol, which hereinafter for the sake of brevity, will be referred to simply as chloroformate ester.

. United States Patent The reaction with phosgene is preferably carried out at a temperature of from 25 C. to about 45 C. with external cooling.

After the chloroformate ester reaction has been completed, as shown by IR analysis, which indicates no further hydroxyl absorption, about 1 mole thereof and from 160 to 200 parts by weight (1.0 to 1.5 moles) of 30% aqueous caustic soda solution, are simultaneously added over a period of /2 to 1 /2 hours at a temperature of 25-50 0, preferably 30-45 C., to an agitating solution of 1 mole of Z-amino-alkane sulfonic acid salt or 1 mole of an N-alkylamino alkane sulfonic acid salt. The addition rates of the reactants are so adjusted as to maintain a pH between 10.5 and 11. Upon completion of the addition, the addition mixture is agitated an additional period of time ranging from 10 to 30 minutes at a temperature of about 35-55 C., then adjusted to a pH of about 9 by means of hydrochloric acid and then cooled to room temperature. The resulting sulfoalkylcarbamate ester, which may be used as the slurry or dried by. conventional means into a powder, shows outstanding detergency characteristics, either alone or in combination with the usual phosphate and silicate builders.

As examples of primary saturated aliphatic alcohols of from 8 to 24 carbon atoms that are first alkoxylated with 3 to 150 moles of either ethyleneoxide, propyleneoxide, butyleneoxide or pentyleneoxide, or mixtures thereof, the following are illustrative: l-octanol, l-nonanol, l-decanol, l-undecanol, l-dodecanol, l-tr-idecanolj, l-tetradecanol, 1-pentadecanol, l-hexadecanol, l-octadecanol, l-nonadecanol, l-eicosanol, l-docosanol, l-tricosanol and ltetracosanol.

As examples of branchedor straight-chained secondary saturated aliphatic alcohols of from 8 to 24 carbon atoms that are alkoxylated with 3 to 150 moles of an alkyleneoxide as above the following are illustrative: 2-octanol, 4-octanol, 2-nonanol, 3-nonanol, 4,6,8-trimethyl-Z-nonanol, 2-decanol, undecanol-S, dodecanol-2, dodecanol-S, tridecanol-2, tridecanol-4, tride'canol- 7, tetradecanol-2, tetradecanol-3, tetradecanol-S, pentadecanol-2, pentadecanol-6, pentadecanol-S, hexadecanol-Z, hexadecanol-7, octadecanol-S, 3-methylheptanol-2; 5-ethylheptanol-2; 2-methylnonanol-4; S-ethylnonanol-Z; 3- ethyl-8-methylnonanol-6; 3-ethylundecanol-6; 7-ethy1-2- methylundecanol-4; 3,9-diethylundecanol-6; S-ethyltridecanol-8; 9-ethyl-5-methyltridecanol-6; 3,9-diethyltridecanol-6; 5,11-diethylpentadecanol-8; 7 ethyl-2 methylundecanol-4; 3,9-diethyltridecanol-6; 5,1l-diethylpentadecanol-8; 7-ethyl-2-methylundecanol-4; 3,9-diethyltridecanol- 6; 5 ,1l-diethylpentadecanol-S, and the like.

Secondary alcohols produced by the'hydrolysis of 2- bromides as well as a mixture of isomeric secondary alcohols obtained by the sulfation of alpha-olefins of from 8 to 20 carbon atoms with sulfuric acid followed by hydrolysis, may also be alkoxylated and utilized in accordance with the present invention.

Secondary alcohols of from 8 to 24 carbon atoms, as well as mixtures thereof prepared in accordance with the teachings of US. Patents 2,088,014-21 may also be employed in the form of their alkoxylated derivatives.

As examples of alkylated phenols that are alkoxylated with 3 to moles of an alkylene oxide, we prefer phenols that contain one or two alkyl substituents of from 4 to 20 carbon atoms, such as, for example, :butylphenol, dibutylphenol, nonylphenol, dinonylphenol, octadecylphenol, di-octadecylphenol, eicosylphenol, and the like.

The alkoxylated primary and secondary aliphatic saturated alcohols of from 8 to 24 carbon atoms and the alkoxylated alkylated phenols utilized in accordance with the present invention are readily prepared by alkoxylating the said alcohols or phenols with ethylene oxide, propylene oxide, butylene oxide, pentylene oxide or with a mixture of such oxides by the usual methods known to the art. Suitable methods are described in United States Patents 1,970,578; 2,203,883; 2,213,477; 2,575,832; 2,593,112; and 2,676,975.

As examples of 2-amino-alkane sulfonic acids that are employed in the form of their alkali metal salts and condensed with the chloroformate ester, the following are illustrative: taurine, N-methyl taurine, N-ethyl taurine, N- propyl taurine, N-isopropyl taurine, N-butyl taurine, N- isobutyl taurine, and N-tert.-butyl taurine.

As examples of N-alkylamino alkane sulfonic acids that are employed in the form of their alkali metal salts, the following are illustrative:

y-(N-methylamino) propane sulfonic acid, y-(N-ethylamino )propane sulfonic acid, y-(N-propylamino) propane sulfonic acid, 'y-(N-butylarnino) propane sulfonic acid, fi-(N-methylamino) butane sulfonic acid, fi-(N-ethylamino) butane sulfonic acid, fi-(N-propylamino) butane sulfonic acid, 6-(N-butylamino) butane sulfonic acid, e-(N-methylamino) pentane sulfonic acid, e-(N-ethylamino) pentane sulfonic acid, e-(N-propylamino) pentane sulfonic acid, and e-(N-butylamino) pentane sulfonic acid, including the corresponding (N-alkylamino)-hexane sulfonic acids.

The sulfoalkylcarbamate esters prepared by the foregoing procedure, while employing the above reactants, are characterized by the following formula:

wherein R is a saturated alkyl of from 8 to 24 carbon atoms, e.g., octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, or a phenyl radical which is substituted by one or two alkyl groups of from 4 to 20 carbon atoms, e.g., butylphenyl, dibutylphenyl, nonylphenyl, dinonylphenyl, octadecylphenyl, di-octadecylphenyl, eicosylphenyl etc., R is either hydrogen or an alkyl of from 1 to 3 carbon atoms, R" is either hydrogen or an alkyl of from 1 to 4 carbon atoms, n is an integer varying from 3 to 150, x is an integer varying from 1 to 5, and M is either hydrogen, or an alkali metal such as sodium, potassium or lithium.

The following examples will illustrate the manner in which the new series of anionic detergents ofthe present invention are obtained:

EXAMPLE I To 332 grams (1.0 mole) of the three mole ethoxylate of oxo-tridecyl-alcohol there were added over one hour at 30-35 C. 108 grams (1.05 moles) of phosgene. The IR spectrum showed no further hydroxyl absorption at this point. The product, the chlorocarbonate of the ethoxylated oxo-tridecylalcohol, was air blown to remove any dissolved HCl or COCI One hundred eighty-five grains (0.47 mole) of the above chloroformate ester and 75 grams of 30% caustic soda solution were simultaneously added over one hour to an agitating solution of 232 grams (0.515 mole) of sodium-N-methyl taurate as its 31% aqueous solution diluted with an additional 150 grams of water. The temperature was maintained at 35-40 C. and the rates of addition adjusted to hold the pH at 10.511.0. Upon completion of the additions, the reaction admixture was agitated at 40 C. for an additional A1 hour, then adjusted to pH 9 by addition of 6 grams of 20 B hydrochloric acid. The activity by methylene blue analysis was 34.4% versus a theoretical activity of 35.1%, indicating 98% conversion of the starting chlorocarbonate ester to the desired sodium-N-methyl-N-sulfoethyl carbamate of ethoxylated oxo-tridecyl alcohol.

The detergent product has a Draves wetting value of 1.55 g./1.; Ross Miles Foam of 113/10 mm. (5 minutes) and a Lime Soap Dispersion value of 10%.

EXAMPLE II To 370 grams (0.8 mole) of the five mole ethoxylate of nonylphenol were added over about one hour at 3040 C. 83 grams (0.84 mole) of phosgene. No further bydroxyl absorption was noted by IR analysis at this point. The product, the chloroformate ester of the ethoxylated nonylphenol was air blown to remove any dissolved HCl or COCI Two hundred ten grams (0.40 mole) of the above chloroformate ester and 65 grams of 30% of sodium hydroxide solution were simultaneously added over a period of one hour at 3045 C. to an agitating solution of 194 grams (0.44 'mole) of sodium-N-methyl taurate as its 31% aqueous solution diluted with an additional 170 grams of water. The addition rates were adjusted to maintain the pH between 10.5 and 11.0. Upon completion of addition, the reaction mixture was agitated an additional hour at 4045 C., then adjusted to pH 9.0 with 4.0 grams of 20 B hydrochloric acid. By methylene blue analysis (S. R. Epstein, Trans. Faraday Society, vol. 44, 226-230 (1948)), the activity of the resultant admixture was 36.5%, indicating a 94% conversion to the N-rnethyl- N-sulfoethylcarbamate of the ethoxylated nonylphenol sodium salt.

The detergent product has a Draves wetting value of 4.0 g./l.; Ross Miles Foam of 135/20 mm. (5 minutes) and a Lime Soap Dispersion of 5 EXAMPLE III Example I was repeated with the exception that the 332 grams of the ethoxylated oxo-tridecylalcohol was replaced with 4670 grams (1 mole) of a secondary eighteen carbon alcohol, i.e., octadecanol-S, ethoxylated to the -mole level with ethylene oxide.

Two thousand one hundred ninety-five grams (0.47 mole) of the above chloroformate ester was reacted as in Example I, substituting 0.515 mole of sodium-N-butyl taurate for the methyl derivative. The resultant sodium- N-butyl-N-sulfoethylcarbaimate of ethoxylated octadecanorl-S was synthesized in 91% yield by methylene blue analysis.

EXAMPLE IV Operating as in Example I, 0.1 mole of the monopropoxylate of eicosylphenol was reacted with a slight excess of phosgene until the disappearance of the hydroxyl function as determined by IR analysis. Again as in Example I, the resultant chloroformate was condensed with 0.1 mole of N-propyl-N-(5-sulfopentyl) amine, as its potas sium salt, to yield 67.0 grams (0.095 mole) of the corresponding eicosylphenol carbamate ester as determined by methylene blue analysis.

EXAMPLE V As in Example I, 103 grams (0.1 mole) of a l-octanol alkoxylate containing an average of 19 moles of ethylene oxide and 1 mole of butylene oxide were reacted with phosgene until disappearance of the hydroxyl function as determined by IR analysis. Operating as in Example I, the resulting chloroformate ester was this time reacted with 15 grams of sodium taurate instead of the equivalent weight of sodium methyl Itaurate' to yield the N-sulfoethyl carbamate ester of the octyl alkoxylate in 96% yield as determined by methylene blue activity.

We claim:

1. A compound having the following formula:

wherein R is a member selected from the group consistmg of alkyl of from 8 to 24 carbon atoms and phenyl, said phenyl containing from one to two alkyl substituents of from 4 to 20 carbon atoms, R is a member selected from the group consisting of hydrogen and alkyl of from 1 to 3 carbon atoms, R is a member selected from the group consisting of hydrogen and alkyl of from 1 to 4 carbon atoms, n is an integer of from 3 to 150, x is an integer of from 1 to 5, and M is a member selected from the group consisting of hydrogen, sodium, potassium and lithium.

2. A compound having the following formula:

1 1 CH -(CH2)12-O-(CHnCHzO)a-NCH CHgsO Na 3. A compound having the following formula:

4. A compound having the following formula:

0 C4110 CH3-(CH2)l7' O-(CHQCHZO)10D yJ-I I CH2CHflSO3Na 5. A compound having the following formula:

where n is an integer of from 3 to 150.

6. A compound having the following formula:

References Cited 10 UNITED STATES PATENTS 2,221,914 11/1940 Engel 260-481 3,086,986 4/1963 011111161 260481 15 FOREIGN PATENTS E. GLEIMAN, Assistant Examiner.

US. Cl. X.R. 252-152; 260-463 

